辉光放电光源在铝合金发射光谱分析上的初步应用

前言辉光放电光源的稳定度高,只要有精度好的检测系统,可保证分析结果有很高的精密度。直接进行固体块样的合金组分元素分析,是这种光源的特长之一。用辉光放电光源作铝合金的分析,国外也有报导。因铝合金极易氧化,试样表面易形成氧化膜,所以试样不易产生正常的剥离,而且预燃时间往往很长又无规律,因而分析再现性不好。浅田庄太郎等认为铝合金的分析,用辉光放电光源是很困难的。他们在试验中还发现了第三元素的影响。试样中只要含有铜,溅射量就增大,使准确度变坏。Dogan研究了铜-     

涂层的辉光放电光谱分析及精密度

本文研究了辉光放电光源的基本特性并应用到涂层表层的组成分析,分析结果和电子探针的结果相一致,证明本方法可靠。辉光放电光源分析的精确度比火花光源有显著的提高,如配用光量计,可进行高含量元素的分析。     

一种新的发射光谱光源辉光放电灯的研制

自从一九六七年Grimm设计了一种结构特殊的辉光放电灯作为发射光谱分析的光源以来,辉光放电光源逐渐引起光谱分析工作者的注意和研究。这种光源的取样和激发机理与惯用的电弧、火花等光源有所不同。它稳定性好,共存元素影响小,谱线自吸收小,并且能对试样表面逐层地取样分析。这使它在高含量合金成份的分析和表层分析方面显示出较大的优越性。我们已研制出这种光源,对它的工作参数、性能及其相互关系进行了初步研究,并与摄谱法配合作了金属表层逐层分析,效果较好。一、设备全部设备由辉光灯、供气系统和稳压电源三部分组成。     

辉光放电质谱法定量测定重掺晶体硅中替位碳含量

采用辉光放电质谱法测定单晶硅中替位碳含量,通过优化仪器工作条件,得到最佳放电参数。利用低温傅里叶变换红外光谱法对呈梯度的四个单晶硅片中替位碳含量进行赋值,将辉光放电质谱法测得替位碳强度与硅的离子束比与赋值结果作工作曲线,计算得到相对灵敏度因子(RSF_(cal))为1.19。在优化过的工作条件下,用辉光放电质谱法测未知样,用RSF_(cal)进行计算,得到单晶硅中替位碳的定量分析结果,与二次离子质谱(SIMS)法测定结果进行对照,相对误差为3.7%,一致性较好。     

微波等离子体增强辉光放电光源激发温度的研究

研究了一种改进型的微波等离子体增强辉光放电光源在光谱分析中的应用，对其重要的参数指标－激发温度进行了较为较细的考察。结果表明引入微波等离子体后辉光放电的激发温度明显高于单纯辉光放电时的激发温度。     

辉光放电光谱法分析掺杂纳米硅薄膜的研究

介绍了利用辉光放电光谱法分析掺杂纳米硅薄膜，通过优化辉光光源激发参数、计算标准样品的溅射率，建立了掺杂纳米硅薄膜的定量表面分析方法。方法应用于实际掺杂纳米硅薄膜样品的分析，并将分析深度、剖析结果与表面形貌仪的结果进行了对照。试验结果表明，分析方法快速、准确，具有实际应用价值。     

射频供能辉光放电原子发射光谱分析导体的基本特性

自行设计组装了射频供能辉光放电原子发射光谱仪器(rf-GD-AES),并对其分析导体试样的基本特性(包括光源的稳定性、电学特性和光谱特性)进行了研究。在此基础上建立了rf-GD-AES分析导电试样的方法,并用于铜合金标准样品中的A l和Mn的分析,其测定结果与标准值吻合很好,充分地显示了rf-GD-AES在固体样品直接分析中的潜力。     

辉光放电光谱法定量分析金属材料表面纳米级薄膜的研究

介绍了利用辉光放电光谱法分析金属材料表面的纳米级薄膜。通过优化辉光光源的放电参数，计算标准样品的溅射率。溅射率经校正后，建立各元素的标准工作曲线，从而形成了纳米级薄膜的定量表面分析方法。试验证明，此方法对膜厚的测定具有很好的准确度和精密度，可应用于多种金属材料表面纳米级薄膜的研究。     

GD-MS法和ICP-MS法测定高纯铌中痕量元素

采用辉光放电质谱法(GD-MS)对高纯铌中Ta,Mo,W等痕量杂质元素进行了测试,并对GD-MS工作参数进行了优化,部分元素与采用电感耦合等离子体质谱法(ICP-MS)定量分析的结果进行比较,对某些元素含量差别较大的原因进行了分析,论述了Element GD辉光放电质谱仪的特点及其在痕量杂质分析上的优势。     

辉光放电质谱法测定纯锡中24种杂质元素和锡记忆效应的消除

采用辉光放电质谱法(GDMS)测定了纯锡中24种杂质元素,分析方法为无标定量分析。分析前纯锡样品须依次用乙醇、水及乙醇冲洗以除去表面的灰尘颗粒,凉干后用于分析。本工作对辉光放电过程中的三项关键因素,即辉光放电电压、放电电流及放电气流三者在辉光放电溅射/电离时的相互关系及其对总离子流强度的影响进行了试验和讨论,并确定了仪器在最佳状态时辉光放电的优化条件为:放电电压590V,放电电流30mA,放电气流450mL·min~(-1)。为排除各元素测定中质谱(MS)干扰的影响,选择了在不同的分辨模式(中/高)下用相对丰度较高、干扰较少的质量数进行分析。所测定元素测定结果的相对标准偏差(n=5)均小于15%。各元素的检出限(3s)为0.003～0.174μg·g~(-1)之间。本方法所得测定结果与电感耦合等离子体原子发射光谱法(ICP-AES)或电感耦合等离子体质谱法(ICP-MS)的测定结果基本一致。经试验,通过更换GDMS的阳极帽、导流管、采样锥和透镜等4种耗材,可完全消除锡的记忆效应。     

Application of thermal analysis to monitor the quality of hypoeutectic cast irons during solidification in sand and metal moulds

By exploring the effects of carbon equivalent (CE?=?3.4?C4.2%) and inoculation (Ca, Ba, Al?CFeSi alloy), the thermal analysis parameters, representative temperatures and undercooling events, during solidification of cast irons are compared with chill tendency (carbides) in cast irons. Cooling curve analyses were conducted directly in the thermal centre of samples solidified in resin sand and metal moulds to explore the utility of thermal analysis in actual casting shapes. As a reference, a Quik-cup? system was employed with the same cooling modulus (CM?=?0.75?cm). The austenite formation temperature is lower at higher CE, with higher temperatures of both the start of the eutectic reaction and end of solidification. This was more pronounced for metal mould solidification and for un-inoculated irons, respectively. The transition from white iron through mottled iron up to grey iron macrostructure is illustrated by variations of eutectic undercooling compared to the metastable equilibrium temperature, as affected by increasing carbon equivalent and applied inoculation. Inoculation affected both austenite and eutectic formation, by preventing excess eutectic undercooling during solidification, even at low carbon equivalent. The differences in solidification patterns of sand and metal mould castings are discussed, for un-inoculated and inoculated irons, at different carbon equivalent values.     

电弧炉燃烧-红外法测定碳量与硫量

电弧炉与红外碳、硫分析仪配套，用于测定硅铁、金属锰、矿石、铬铁、钒铁、合金钢铸铁、水泥、微晶玻璃，阳极泥等物质中碳量和硫量，结果满意。     

The determination of carbon,phosphorus and sulphur in steel and cast iron with a glow-discharge emission source and an atomic fluorimeter as spectral line isolator

The atomic fluorimeter, an instrument using an atomic vapour generated by cathodic sputtering for isolating resonance spectral lines emitted by an emission source, was used for detecting the vacuum ultraviolet emission lines of carbon, phosphorous and sulphur. A glow-discharge lamp was used as emission source. Detection limits of 0.012, 0.004 and 0.002% were obtained for carbon, phosphorus and sulphur respectively in cast iron and steel. A narrow-band interference filter through which the matrix emission was measured directly by a photomultiplier tube, was used in an effort to correct for varying sputtering rates from different kinds of samples. This monitoring channel proved to be efficient for the determination of phosphorus and carbon in high alloy steels, but was not necessary for sulphur since in this case working curves of the different types of steels coincided.     

火花放电原子发射光谱法测定钛及钛合金中主要元素

采用火花放电原子发射光谱法测定了钛及钛合金中碳、铁、铝和钒的含量。通过对钛合金样品的表面处理方式、氩气流量和压力、类型标准化等参数的摸索,确立了一套系统的分析方法。结果表明,4种元素测定的相对标准偏差在0.40%~6.8%,测定结果和化学湿法分析结果相比基本一致,比较适合批量检测。     

Determination of trace levels of iron in a seawater sample using isotope dilution/inductively coupled plasma mass spectrometry.

An analytical method for trace levels of iron in a seawater sample using isotope dilution ICP-MS was developed. Preconcentration of iron and the removal of major elements in seawater such as alkali and alkaline-earth elements can be carried out quickly using a chelating resin disk by adjusting the sample pH to 3. The collision cell option of the ICP-MS instrument method was used to improve the performance of the instrument for iron measurements since ArO and ArN interferences could be reduced using this analytical method. About 4 ml min(-1) helium, as the collision gas, were introduced into the cell. 40Ar14N and 40Ar16O which interfere with 54Fe and 56Fe in water had their amounts decreased by 5 orders of magnitude. Then, the isotope dilution method was used for iron determination below ng g(-1) level of trace iron in four environmental reference materials (river water standard sample JAC-0031 (Japan Soc. for Analytical Chemistry), estuarine standard sample SLEW-2 (NRC Canada) and seawater standard samples CASS-3 and NASS-5 (NRC Canada)) were measured. Good agreement between analytical results and certified values of reference materials was obtained, which confirmed the effectiveness of this method.     

火花激发原子发射光谱分析不锈钢线材

火花激发原子发射光谱法应用于直径小于8mm的不锈钢线材的分析，对此类试样应用了一种特制的夹具，用块状标准样品制作工作曲线。由于线状试样和块状标准样品之间的形状差异所产生的系统不确定度借采用同类型标样作校正，对共存元素的相互干扰也采用了相应的校正方法。其它分析条件，包括严格的制样工序，氩气的纯度要求及其流量控制，以及光源的最佳条件等，作了深入的试验。按所提出的方法测定了不锈钢线材试样中碳、硅、锰、磷、硫、铬、镍及钛等8个元素。经校正后的结果与化学法测得结果相符。     

Direct Quantification of Major and Trace Elements in Geological Samples by Time-of-Flight Mass Spectrometry with a Pulsed Glow Discharge

A method has been developed for the determination of 24 elements (As, B, Ce, Co, Dy, Fe, K, La, Lu, Mg, Mn, Na, Nb, Nd, P, Pr, Rb, S, Sb, Si, Sm, Th, Ti, and U) in ore samples by pulsed direct current glow discharge time-of-flight mass spectrometry (PGD-TOF-MS). Sample treatment consisted of pressing the powdered samples into 10?mm diameter aluminum tablets. Quantification was performed using relative sensitivity factors with iron as the normalization element. PGD-TOFMS has low spectral interferences and low limits of detection and provides the quantification of the wide range of elements with a single method instead of a combination of several techniques. The limits of detection of the designed method were in the range 2–4?×?10^?6 mass %, depending on the element. The designed procedure was validated by the analysis of standard reference materials. The obtained results showed adequate repeatability (6–9% relative standard deviation), demonstrating high efficiency of the glow discharge mass spectrometry for the direct analysis of geological samples. The designed method requires a minimal sample pretreatment and is applicable for the determination of wide range of elements of the periodic table (e.g., metals, nonmetals, and rare earth elements) in a single analytical procedure without sample dissolution with adequate accuracy, sensitivity, and repeatability. The designed approach may replace the complex techniques that are normally required for this task.     

用混合熔剂熔融制样-XRFS法分析铁矿石方法改进的探讨

针对XRFS法分析铁矿石时存在的总铁量及硫量测定结果的不准确问题，作了进一步试验并对方法提出了修改。其要点是采用了加入含钴的四硼酸锂和碳酸锂的混合熔剂熔融试样，并对熔融温度及时作了规定，采用钴的谱线作内标，以及根据总铁量的高低分别采用两条工作曲线。此外，对同时含钒及钛的试样，采用校正方法消除其相互间的干扰，按修改后的方法分析铁矿石试样，结果的准确度和精密度均达到规定要求。     

火花放电原子发射光谱法测定镍基合金中12种元素

化学元素的含量及其变化影响镍基合金材料的各项性能。因此准确检测镍基合金化学成分并对其严格控制,对提高和保证镍基合金材料性能具有重要意义。通过对仪器分析条件进行优化,采用控制样品法,建立了用火花放电原子发射光谱法测定镍基合金中Al、C、Cr、Co、Cu、Fe、Nb、P、Si、S、W、Mo等12种元素含量的方法。采用优化的吹氩时间6 s、预燃时间6 s、积分时间8 s等实验条件测定了3种常规镍基合金样品,测定值与现行国家标准分析方法结果一致。     

Enhancement of intensities in glow discharge mass spectrometry by using mixtures of argon and helium as plasma gases

Glow discharge mass spectrometry (GD-MS) is an excellent technique for fast multi-element analysis of pure metals. In addition to metallic impurities, non-metals also can be determined. However, the sensitivity for these elements can be limited due to their high first ionization potentials. Elements with a first ionization potential close to or higher than that of argon, which is commonly used as discharge gas in GD-MS analysis, are ionized with small efficiency only. To improve the sensitivity of GD-MS for such elements, the influence of different glow-discharge parameters on the peak intensity of carbon, chlorine, fluorine, nitrogen, phosphorus, oxygen, and sulfur in pure copper samples was investigated with an Element GD (Thermo Fisher Scientific) GD-MS. Discharge current, discharge gas flow, and discharge gas composition, the last of which turned out to have the greatest effect on the measured intensities, were varied. Argon–helium mixtures were used because of the very high potential of He to ionize other elements, especially in terms of the high energy level of its metastable states. The effect of different Ar–He compositions on the peak intensity of various impurities in pure copper was studied. With Ar–He mixtures, excellent signal enhancements were achieved in comparison with use of pure Ar as discharge gas. In this way, traceable linear calibration curves for phosphorus and sulfur down to the μg kg⁻¹ range could be established with high sensitivity and very good linearity using pressed powder samples for calibration. This was not possible when pure argon alone was used as discharge gas. This contribution is based on a presentation given at the Colloquium for Analytical Atomic Spectroscopy (CANAS ’07) held March 18–21, 2007 in Constance, Germany.